TW201805342A - Curable composition and cured product of same - Google Patents

Abstract

Provided is a curable composition which is capable of forming a cured product that has excellent acid resistance, flexibility and adhesion properties. This curable composition contains a (meth)allyl group-containing compound (A) having two or more (meth)allyl groups in one molecule, a thiol compound (B) having two or more mercapto groups in one molecule, at least one compound (C) selected from among epoxy (meth)acrylates, (poly)ester (meth)acrylates and unsaturated polyester resins, and a polymerization initiator (D).

Description

Hardening composition and hardened material thereof

The present invention relates to a curable composition and a cured product thereof.

The photosensitive resin composition is used for manufacture of a printed wiring board or a glass substrate. When a printed wiring board is manufactured, a photoresist image formed of a cured product that is cured by exposing the photosensitive resin composition must have sufficient acid resistance because it is exposed to an acidic etching solution or a plating solution. In addition, when the burr formed on the cut end surface of the glass substrate is removed with an etching solution, in order to protect the transparent conductive material on the glass substrate with a protective mask made of a cured material that is cured by exposing the photosensitive resin composition. Film or flexible printed circuit board, protective mask must have sufficient acid resistance.

Patent Documents 1 and 2 disclose protection materials having acid resistance. However, there is a problem in that protection of the protection object cannot be performed due to insufficient acid resistance, flexibility, and insufficient adhesion to the protection object.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 351214

[Patent Document 2] International Publication No. 2013/011770

Therefore, an object of the present invention is to provide a hardenable composition capable of forming a hardened material excellent in acid resistance, softness, and adhesion, by solving the problems of the conventional techniques described above. It is another object of the present invention to provide a cured product excellent in acid resistance, flexibility, and adhesion.

In order to solve the aforementioned problems, one aspect of the present invention is as follows [1] to [11].

[1] A sclerosing composition comprising a (meth) allyl-containing compound (A) having two or more (meth) allyl groups in one molecule, and a compound having 2 in one molecule. More than one mercapto thiol compound (B), and at least one compound (C) selected from epoxy (meth) acrylate, (poly) ester (meth) acrylate, and unsaturated polyester resin, With polymerization initiator (D).

[2] The curable composition according to [1], wherein the (meth) allyl-containing compound (A) includes at least one structure selected from an alicyclic structure, an aromatic ring structure, and a heterocyclic structure. Of compounds.

[3] The curable composition according to [1], wherein the composition contains (a (A) yl) allyl compound (A) includes a compound having a bisphenol A type skeleton.

[4] The curable composition according to [1], wherein the (meth) allyl-containing compound (A) includes a compound having at least one of an allyloxycarbonyl group and an N-allyl group.

[5] The curable composition according to any one of [1] to [4], wherein the thiol compound (B) includes two or more thiol groups in one molecule and all of the thiol groups are bonded to a secondary carbon. Atomic or tertiary carbon atoms.

[6] The curable composition according to any one of [1] to [4], wherein the thiol compound (B) includes a compound having a group represented by the following formula (1); 1) R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m represents an integer of 0 to 2;

-2,4,6(1H,3H,5H)-三 酮及三羥甲基丙烷三(3-巰基丁酸酯)所選出的至少1者。 [7] The hardenable composition according to any one of [1] to [4], wherein the thiol compound (B) includes 1,4-bis (3-mercaptobutoxy) butane and pentaerythritol Tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutoxyethyl) -1,3,5-tris

-2,4,6 (1H, 3H, 5H) -trione and at least one selected from trimethylolpropane tris (3-mercaptobutyrate).

[8] The curable composition according to any one of [1] to [7], wherein the compound (C) includes a compound having at least one structure selected from an alicyclic structure, an aromatic ring structure, and a heterocyclic structure. Compound.

[9] The curable composition according to any one of [1] to [7], wherein the compound (C) includes a compound having a bisphenol A type skeleton.

[10] The curable composition according to any one of [1] to [9], wherein the number of (meth) allyl groups of the (meth) allyl-containing compound (A) is relative to the number of The ratio of the number of thiol groups (the number of allyl groups / the number of thiol groups) of the thiol compound (B) is in the range of 0.25 or more and 4 or less. The (meth) allyl-containing compound (A) and the When the total content of the thiol compound (B) and the aforementioned compound (C) is taken as 100 parts by mass, the content of the aforementioned compound (C) is 10 to 70 parts by mass, and the amount of the aforementioned polymerization initiator (D) The content is 0.01 to 10 parts by mass.

[11] A cured product, which is a cured product of the curable composition according to any one of [1] to [10].

The curable composition of the present invention can form a cured product having excellent acid resistance, flexibility, and adhesion. The cured product of the present invention is excellent in acid resistance, flexibility, and adhesion.

[Mode for Carrying Out the Invention]

An embodiment of the present invention will be described. The curable composition according to this embodiment contains (meth) allyl-containing compound (A) having two or more (meth) allyl groups in one molecule, and two or more in one molecule. Thiol thiol compound (B), and at least one compound (C) selected from epoxy (meth) acrylate, (poly) ester (meth) acrylate, and unsaturated polyester resin, and polymerize Initiator (D).

The curable composition of this embodiment can be easily cured in a short time by irradiation with active energy rays, and the cured product has excellent acid resistance, softness, and adhesion. Therefore, the curable composition of the present embodiment can be suitably used as an etching protection material for protecting an acidic etching solution or a plating protection material for protecting an acidic plating solution. In addition, it can be used as a casting material, a coating material, a molding material, and the like in various other industrial fields.

Hereinafter, a curable composition according to an embodiment of the present invention and a cured product obtained by irradiating the curable composition with active energy rays will be described in detail.

In the present specification, "(meth) allyl" means methallyl (ie, 2-methyl-2-propenyl) and / or allyl (ie, 2-propenyl) . The "(meth) acrylate" means a methacrylate and / or an acrylate, and the "(meth) acrylfluorenyl" means a methacrylfluorenyl and / or acrylfluorenyl.

[1] (Meth) allyl-containing compound (A) having two or more (meth) allyl groups in one molecule

The (meth) allyl-containing compound (A) may be a monomer, an oligomer, or a polymer. From the viewpoint of viscosity, it is preferably a number average molecular weight of 200 to 20,000. Compound. The molecular weight of the oligomer or polymer in the present invention is a number-average molecular weight in terms of polystyrene (PS) as measured by gel permeation chromatography (GPC method) unless otherwise specified in advance.

Examples of the (meth) allyl-containing compound (A) include a compound (a-1) and a compound having at least one structure selected from an alicyclic structure, an aromatic ring structure, and a heterocyclic structure in the molecule. The cyclic compound (a-2).

環、源自於三聚氰酸的環、源自於異三聚氰酸的環等。 Examples of the alicyclic structure include an alicyclic ring having 3 to 6 carbon atoms, and a cyclohexane ring and a cycloheptane ring are preferred. Examples of the aromatic ring structure include an aromatic ring having 6 to 10 carbon atoms, and a benzene ring and a naphthalene ring are preferred. Examples of the heterocyclic structure include a three-membered ring to a ten-membered ring having a nitrogen atom, an oxygen atom, or a sulfur atom, and examples thereof include a pyridine ring and a three-membered ring.

Ring, ring derived from cyanuric acid, ring derived from isocyanuric acid, and the like.

、1,3,4,6-四烯丙基甘脲等之具有雜環構造的含有N-烯丙基的化合物。 When the (meth) allyl-containing compound (A) is a monomer, examples of the compound (a-1) include diallyl phthalate, diallyl isophthalate, and p-benzene Allyloxycarbonyl group-containing compounds having an aromatic ring structure such as diallyl dicarboxylate, triallyl trimellitate, tetraallyl trimellitate, bisphenol A diallyl ether, or Diallyl 1,2-cyclohexanedicarboxylate, diallyl 1,3-cyclohexanedicarboxylate, diallyl 1,4-cyclohexanedicarboxylate, 1,2,4 -Triallyl cyclohexanetricarboxylic acid, tetraallyl 1,2,4,5-cyclohexanetetracarboxylic acid, 5-alkyl substituted cyclohexane-1,4-dicarboxylic acid diallyl Ester, 5-halo substituted cyclohexane-1,4-dicarboxylic acid diallyl, 1,3-adamantane dicarboxylic acid diallyl, 1,3,5-adamantane tricarboxylic acid triallyl Ester, hydrogenated bisphenol A diallyl ether, hydrogenated dimer acid (36 or 44 carbons, alicyclic structure) diallyl ester, tricyclodecane dimethanol dicarboxylic acid diallyl ester, etc. Allyloxycarbonyl group-containing compound having an alicyclic structure, or triallyl isocyanurate, triallyl tricyanate, diallyl monohydroxyethyl Polycyanate, diallyl monohydroxyethyl isotricyanate, diallyl isotricyanate, triallyl isotricyanate prepolymer, 1, 3, 5 -Triallylhexahydro-1,3,5-tri

N-allyl-containing compounds having a heterocyclic structure such as 1,3,4,6-tetraallyl glycoluril and the like.

、1,3,4,6-四甲基烯丙基甘脲等之含有N-甲基烯丙基的化合物。 In addition, dimethylallyl phthalate, dimethylallyl isophthalate, dimethylallyl terephthalate, trimethylallyl trimellitate, benzene Tetramethylallyl tetramethallyl, bisphenol A dimethylallyl ether, and the like having a methallyloxycarbonyl group-containing compound having an aromatic ring structure, or 1,2-cyclohexanedicarboxylic acid di Methyl allyl ester, dimethyl allyl 1,3-cyclohexanedicarboxylate, dimethyl allyl 1,4-cyclohexane dicarboxylate, 1,2,4-cyclohexane tri Trimethylallyl carboxylate, tetramethylallyl 1,2,4,5-cyclohexanetetracarboxylate, dimethylene with 5-alkyl substituted cyclohexane-1,4-dicarboxylic acid Propyl ester, 5-halo substituted cyclohexane-1,4-dicarboxylic acid dimethyl allyl ester, 1,3-adamantane dicarboxylic acid dimethyl allyl ester, 1,3,5-adamantane tri Trimethylallyl carboxylic acid, 5-halo substituted cyclohexane-1,4-dicarboxylic acid dimethylallyl ester, hydrogenated dimer acid (36 or 44 carbon atoms, alicyclic structure) Methylallyloxycarbonyl group-containing compounds having an alicyclic structure, such as methallyl ester, dimethylallyl tricyclodecane dimethanol dicarboxylate, or trimethyl isocyanurate Allyl allyl, trimethyl allyl tricyanate, 1,3,5-trimethylallyl hexahydro-1,3,5-tri

, 1,3,4,6-tetramethylallyl glycoluril and other compounds containing N-methylallyl.

Examples of the compound (a-1) include bisphenol A diallyl ether, bisphenol A dimethylallyl ether, bisphenol S diallyl ether, and bisphenol S dimethylene. Propyl ether, 1,4-naphthalenedicarboxylic acid diallyl ether, 1,4-naphthalenedicarboxylic acid diallyl ether, 1,5-naphthalenedicarboxylic acid diallyl ether, 1, Dimethylallyl ether of 5-naphthalenedicarboxylic acid, diallyl ether of 2,6-naphthalenedicarboxylic acid, dimethylallyl ether of 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid Diallyl carboxylic acid ether, 2,7-naphthalenedicarboxylic acid dimethyl allyl ether, diphenyl-m, m'-dicarboxylic acid diallyl ether, diphenyl-m, m ' -Dimethylallyl ether of dicarboxylic acid, diphenyl-p, p'-dicarboxylic acid diallyl ether, diphenyl-p, p'-dicarboxylic acid dimethylallyl ether, Diphenylketone-4,4-dicarboxylic acid diallyl ether, diphenylketone-4,4-dicarboxylic acid dimethylallyl ether, methyl terephthalate diallyl ether, Dimethylallyl terephthalate, diallyl ether tetrachlorophthalate, dimethylallyl ether tetrachlorophthalate, diallyl hydrazone, dimethylene Propyl fluorene, fluorene bisphenoxyethyl diallyl ether, fluorene bisphenoxyethyl Dimethyl allyl ether, fluoren bisphenoxyethyl dimethyl allyl ether, fluoren bisphenoxy ethyl dimethyl allyl ether, fluoren bisphenoxy dimethyl allyl ether Allyl ether compounds and the like.

、1-烯丙基-3,5-二甲基烯丙基六氫-1,3,5-三

、1,3,4,6-甲基烯丙基三烯丙基甘脲、1,3,4,6-二甲基烯丙基二烯丙基甘脲、1,3,4,6-三甲基烯丙基烯丙基甘脲等之N-甲基烯丙基與N-烯丙基共存之化合物。 On the other hand, a compound having an allyl group and a methallyl group in one molecule is also mentioned. Examples of the compound (a-1) include allyl methallyl phthalate, allyl methallyl isophthalate, and diallyl methallyl trimellitate , Allyl dimethyl allyl trimellitate, triallyl methallyl trimellitic acid, diallyl dimethyl allyl pyromellitic acid, allyl trimellitate Trimethylallyl ester, bisphenol A allyl methyl allyl ether, bisphenol S allyl methyl allyl ether, 1,4-naphthalenedicarboxylic acid allyl methyl allyl Ether, 1,5-naphthalenedicarboxylic acid allyl methyl allyl ether, 2,6-naphthalenedicarboxylic acid allyl methyl allyl ether, 2,7-naphthalenedicarboxylic acid allyl methyl Allyl ether, diphenyl-m, m'-dicarboxylic allyl methyl allyl ether, diphenyl-p, p'-dicarboxylic allyl methyl allyl ether, Diphenyl ketone-4,4-dicarboxylic acid allyl methyl allyl ether, methyl terephthalate allyl methyl allyl ether, allyl methyl phthalate Aromatic rings such as propyl ether, allyl methyl allyl hydrazone, fluoren bisphenoxyethyl allyl methyl allyl ether, fluoren bisphenoxy allyl methyl allyl ether Construct Methallyl and allyl coexisting compounds, or allyl methyl allyl 1,4-cyclohexanedicarboxylic acid, allyl methyl 1,3-cyclohexane dicarboxylic acid Allyl ester, 1,2,4-cyclohexane tricarboxylic acid allyl dimethyl allyl ester, 1,2,4-cyclohexane tricarboxylic acid allyl dimethyl allyl ester, 1, Triallylmethylallyl 2,4,5-cyclohexanetetracarboxylic acid, diallyldimethylallyl 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2 , 4,5-cyclohexane tetracarboxylic allyltrimethylallyl ester, 5-alkyl substituted cyclohexane-1,4-dicarboxylic acid allyl methyl allyl ester, 5-halogen substituted Allyl methyl allyl cyclohexane-1,4-dicarboxylate, allyl methyl allyl 1,3-adamantane dicarboxylate, 1,3,5-adamantane tricarboxylic acid di Allyl methyl allyl, 1,3,5-adamantane tricarboxylic acid allyl dimethyl allyl, hydrogenated dimer acid (36 or 44 carbon atoms, alicyclic structure) allyl Compounds in which allyl and allylic groups coexist with an alicyclic structure, such as methylmethylallyl ester, allylmethylallyl tricyclodecane dimethanol dicarboxylate, or allylmethyl Allyl monohydroxyethyl cyanurate, diene Methylmethyl allyl isotricyanate, allyl dimethyl allyl isotricyanate, 1,5-diallyl-3-methylallyl hexahydro-1, 3,5-three

, 1-allyl-3,5-dimethylallylhexahydro-1,3,5-tri

, 1,3,4,6-methylallyl triallyl glycoluril, 1,3,4,6-dimethylallyl diallyl glycoluril, 1,3,4,6- A compound in which N-methylallyl and N-allyl coexist, such as trimethylallyl allyl glycoluril.

Examples of the compound (a-2) include diethylene glycol bis (allyl carbonate), tetraallyl 1,2,3,4-butanetetracarboxylic acid, diallyl succinate, and glutaric acid Diallyl acid, diallyl adipate, diallyl sebacate, diallyl dimer, diallyl hydrogenated dimer, 1,12-dodecanediene diene Propyl ester, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, trimethylolpropane triallyl ether, pentaerythritol tetraallyl ether, diethylene glycol bis (methylallyl carbonate (Ester), 1,2,3,4-butane tetracarboxylic acid tetramethylallyl ester, dimethylallyl succinate, dimethylallyl glutarate, dimethylallyl adipate Ester, dimethylallyl sebacate, dimethylallyl dimer, dimethylallyl hydrogenated dimer, dimethylallyl 1,12-dodecanedioate, three Methylolpropane dimethylallyl ether, pentaerythritol trimethylallyl ether, trimethylolpropane trimethylallyl ether, pentaerythritol tetramethylallyl ether, and the like.

Considering the cured product of the curable composition of this embodiment If it is acid resistant, the compound (a-1) is superior to the compound (a-2). When the compound (A) containing a (meth) allyl group is a monomer, or a (meth) olefin containing a methyl group will be described later. The same applies when the propyl compound (A) is an oligomer. In addition, in consideration of the reactivity (active energy ray hardenability) of the curable composition, among these (meth) allyl-containing compounds (A), those having an allyloxycarbonyl group and A compound of at least one of N-allyl. In addition, those having extremely strong acidic corrosion resistance are particularly excellent in being a (meth) allyl-containing compound (A) having a bisphenol A type skeleton, and a commercially available product may be represented by the following formula (2) The product name is CM-BPADE manufactured by Chembridge.

When the (meth) allyl-containing compound (A) is an oligomer, the (meth) allyl-containing compound (A) includes a (meth) allyl ester resin. The so-called (meth) allyl ester resin is a compound having a (meth) allyloxycarbonyl group at a molecular terminal and a repeating unit in the molecule. For example, by a transesterification reaction of a poly (meth) allyl ester compound of a polyacid with a polyhydric alcohol, a unit alcohol containing a (meth) allyl allyl alcohol, a polyhydric alcohol, and at least One type of condensation reaction, transesterification reaction of a polyhydric alcohol having a repeating unit and a (meth) allyl ester compound of a polyacid, a unit alcohol containing a (meth) allyl allyl alcohol, and a polyhydric having a repeating unit Alcohol and polyacid A compound produced by various reactions of at least one selected condensation reaction of an anhydride.

Specific examples of the (meth) allyl ester resin include an oligomer having a structure represented by the following formulae (3), (4), and (6).

The j R ³ groups in the formula (3) each independently represent a linear or branched alkylene group having 1 to 36 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms). R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group. Both R ⁴ and R ⁵ are preferably hydrogen atoms.

The (j + 1) X's in the formula (3) are each independently an organic group derived from a divalent carboxylic acid, and are preferably phenylene which may have an alkyl group having 1 to 4 carbon atoms as a substituent. Or a cyclohexyl group, more preferably a phenyl or cyclohexyl group having no substituent. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, isobutyl, and third butyl.

The position at which the phenylene or cyclohexyl group is bonded to the adjacent carbonyl carbon may be any of 1, 2, 1, 3, and 1, and if the ease of synthesis is considered, it is preferably 1, 3 or 1, 4 digits.

J in the formula (3) is an integer of 1 or more and 20 or less, preferably 1 or more and 18 or less, and more preferably 1 or more and 15 or less. Oligomer represented by formula (3) The molecular weight of the polymer is preferably from 300 to 20,000, more preferably from 800 to 18,000, and even more preferably from 1,000 to 16,000.

The (2k + 1) A's in formula (4) are each independently an organic group derived from a divalent carboxylic acid, and are preferably a phenylene group which may have an alkyl group having 1 to 4 carbon atoms as a substituent or The cyclohexyl group is more preferably a phenylene group or a cyclohexyl group having no substituent. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, isobutyl, and third butyl.

The position at which the phenylene or cyclohexyl group is bonded to the adjacent carbonyl carbon may be any of 1, 2, 1, 3, and 1, and if the ease of synthesis is considered, it is preferably 1, 3 or 1, 4 digits.

K R ⁶ in formula (4) each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, n-butyl, (Dibutyl, isobutyl, third butyl) or a group represented by the following formula (5). In addition, R ⁷ , R ⁹ and k R ^{8 in} formula (4) each independently represent a hydrogen atom or a methyl group. Preferably, R ⁷ , R ⁹ and K R ^{8 are} all hydrogen atoms. The A system in the formula (5) is the same as in the case of the oligomer represented by the formula (4), and R ¹⁰ represents a hydrogen atom or a methyl group. R ^{10 is} preferably a hydrogen atom.

K in the formula (4) is an integer of 3 or more and 70 or less, preferably 4 or more and 60 or less, and more preferably 4 or more and 50 or less. The molecular weight of the oligomer represented by the formula (4) is preferably 300 or more and 20,000 or less, more preferably 500 or more and 18,000 or less, and even more preferably 700 or more and 16,000 or less.

The (q + 1) Zs in the formula (6) are each independently an organic group derived from a divalent carboxylic acid, and are preferably a phenylene group which may have an alkyl group having 1 to 4 carbon atoms as a substituent or The cyclohexyl group is more preferably a phenylene group or a cyclohexyl group having no substituent. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, isobutyl, and third butyl.

[(P + 1) × q] R ^{11 in} formula (6) each independently represents a linear alkylene having a carbon number of 1 or more and 36 or less (preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less). Radical or branched alkylene. R ¹² and R ¹³ in formula (6) each independently represent a hydrogen atom or a methyl group. Both R ¹² and R ¹³ are preferably hydrogen atoms.

P in the formula (6) is an integer of 1 or more and 10 or less, preferably 1 or more and 9 or less, and more preferably 1 or more and 8 or less. Q in Formula (6) is an integer of 5 or more and 50 or less, Preferably it is 5 or more and 45 or less, More preferably, it is 5 or more and 40 or less. The molecular weight of the oligomer represented by the formula (6) is preferably 300 or more and 20,000 or less, more preferably 500 or more and 19,000 or less, and even more preferably 700 or more and 18,000 or less.

Specific examples other than the (meth) allyl resin when the (meth) allyl-containing compound (A) is an oligomer include polyenes derived from substituted or unsubstituted allyl alcohol Compounds, polyethylene glycol bis (allyl carbonate), and the like.

When the (meth) allyl-containing compound (A) is a polymer, examples of the (meth) allyl-containing compound (A) include two or more allyls introduced into a polymer skeleton. Of the compound. Examples of the polymer skeleton include a polyethylene skeleton, a polyurethane skeleton, a polyester skeleton, a polyamidamine skeleton, a polyamidoimide skeleton, a polyoxyalkylene skeleton, and a polyphenylene styrene skeleton.

The (meth) allyl-containing compound (A) may be used alone or in combination of two or more.

The iodine value of the mixture containing all the compounds of the (meth) allyl-containing compound (A) used in the curable composition belonging to this embodiment is preferably in the range of 20 or more and 240 or less. Preferably it is 30 or more and 210 or less. If the iodine value is in the range of 20 to 240, the hardening can be easily performed in a short time by irradiation with active energy rays. Sexual composition hardens. The iodine value described in the present specification is a value obtained by converting the amount of halogen (unit: g) that reacts with 100 g of the target substance into grams of iodine.

[2] Thiol compound (B) having two or more mercapto groups in one molecule

The thiol compound (B) is preferably a compound having two or more and six or less mercapto groups in the molecule. For example, aliphatic polythiols such as alkanedithiols having 2 to 20 carbons, aromatic polythiols such as xylylene dithiol, and alcohols substituted with thiol groups can be mentioned. Polythiols made from halogen atoms of halogenated alcohol adducts, and polythiols made from hydrogen sulfide reaction products of polyepoxide compounds. From the viewpoint, it is preferably formed from an esterified product of a polyhydric alcohol having two or more and six or less hydroxyl groups in the molecule and a thiocarboxylic acid typified by mercaptoacetic acid, β-mercaptopropionic acid, and β-mercaptobutyric acid. Polythiol.

The thiol compound (B) is particularly preferably a compound having two or more thiol groups in one molecule and all of the thiol groups are bonded to a secondary carbon atom or a tertiary carbon atom. That is, the thiol compound (B) is a thiol compound having a thiol group-containing group having a substituent bonded to a carbon atom at the α position of the thiol group, and having two or more thiol groups. At least one of the aforementioned substituents is preferably an alkyl group. A compound in which all of the thiol groups are bonded to a secondary carbon atom or a tertiary carbon atom is superior in water resistance compared to a compound in which the thiol group is bonded to a primary carbon atom, so that the acid resistance is also excellent.

The so-called substituent is bonded to the carbon atom at the alpha position for the mercapto group Above, it means that the carbon at the alpha position of the mercapto group is bonded to 2 or 3 carbon atoms. When at least one of the aforementioned substituents is an alkyl group, it means that among the groups bonded to a carbon atom at the α position with respect to a mercapto group, at least one of the groups other than the main chain is an alkyl group. Here, the main chain refers to a structural site having the longest chain among structural sites other than a mercapto group and a hydrogen atom of a carbon atom bonded to an α position.

The mercapto group-containing group is preferably a group represented by the following formula (1). However, R ¹ in the following formula (1) represents an alkyl group having 1 to 10 carbon atoms, and R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. In addition, m in the following formula (1) represents an integer of 0 to 2 and is preferably 0 or 1.

The alkyl system having 1 to 10 carbon atoms represented by R ¹ and R ² may be linear or branched. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, third butyl, n-hexyl, n-octyl, and the like, and methyl or ethyl is preferred.

The thiol compound (B) is not particularly limited as long as it is a compound in which all of the thiol groups are bonded to a secondary carbon atom or a tertiary carbon atom and has two or more thiol groups, but preferably has two or more of the above-mentioned thiols. A multifunctional thiol compound with a mercapto group.

As described above, since the thiol compound (B) is polyfunctional, the sensitivity of the active energy ray hardenability (photopolymerization) can be improved compared with a monofunctional compound.

The thiol group-containing group is more preferably a group having a carboxylic acid derivative structure represented by the following formula (7).

The thiol compound (B) is preferably an ester of a mercapto group-containing carboxylic acid and an alcohol represented by the following formula (8).

The definitions of R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ in Formula (7) and Formula (8) are the same as the definitions of R ¹ and R ² in Formula (1), and the definitions of r and s are the same as The definition of m in the above formula (1) is the same.

As the alcohol esterified with the mercapto group-containing carboxylic acid represented by the formula (8), a polyhydric alcohol is preferred. By using a polyhydric alcohol, the compound obtained by the esterification reaction can be made into a polyfunctional thiol compound.

Examples of the polyhydric alcohol include alkanediol (but The carbon number is 2 or more and 10 or less, and the carbon chain system may be linear or branched), diethylene glycol, glycerol, dipropylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol . Examples of the alkanediols include ethylene glycol, trimethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, and tetraethylene glycol. Methylene glycol.

Among these, trimethylolpropane, pentaerythritol, and tri (2-hydroxyethyl) isotricyanate are also preferable from the viewpoints of easy availability, number of functional groups, or vapor pressure.

Examples of the mercapto group-containing carboxylic acid of the formula (8) include 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptobutyric acid, 3-mercaptobutyric acid, 4-mercaptobutyric acid, and 2-mercaptoisobutyl Acids, 2-mercapto isovaleric acid, 3-mercapto isovaleric acid, 3-mercapto isovaleric acid, and the like.

Specific examples of the compound having two or more thiol group-containing groups of the above formula (1) and all of the thiol groups are bonded to a secondary carbon atom or a tertiary carbon atom include the following compounds.

Examples of the hydrocarbon dithiol include 2,5-hexanedithiol, 2,9-decanedithiol, 1,4-bis (1-mercaptoethyl) benzene, and the like.

-2,4,6(1H,3H,5H)-三酮等。 Examples of the thiol compound (B) containing an ester bond structure include bis (1-mercaptoethyl) phthalate, bis (2-mercaptopropyl) phthalate, and bis (3-mercapto) phthalate. Butyl ester), ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercapto Butyrate), octanediol bis (3-mercaptobutyrate), trimethylolpropane tri (3-mercaptobutyrate), pentaerythritol tetra (3-mercaptobutyrate), dipentaerythritol hexa (3- Mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2 -Mercaptopropionate), octanediol bis (2-mercaptopropionate), trimethylolpropane tri (2-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate), dipentaerythritol hexa ( 2-mercaptopropionate), ethylene glycol bis (4-mercaptovalerate), propylene glycol bis (4-mercaptoisovalerate), diethylene glycol bis (4-mercaptovalerate), butanediol Bis (4-mercaptovalerate), octanediol bis (4-mercaptovalerate), trimethylolpropane tris (4-mercaptovalerate), pentaerythritol tetrakis (4-mercapto) Acid ester), dipentaerythritol hexa (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), propylene glycol bis (3-mercaptovalerate), diethylene glycol bis (3-mercaptopentyl) Acid ester), butanediol bis (3-mercaptovalerate), octanediol bis (3-mercaptovalerate), trimethylolpropane tri (3-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate) (Mercaptovalerate), dipentaerythritol hexa (3-mercaptovalerate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutoxyethyl) Base) -1,3,5-tri

-2,4,6 (1H, 3H, 5H) -trione and the like.

Regarding the mercapto group, the radical polymerization or ionic polymerization of a thiol compound having a substituent other than hydrogen at the α-position and / or the β-position is calculated. Activation energy (298K, 1 atmosphere) of a secondary thiol structure having a methyl group at the alpha position. That is, the activation energy of the secondary thiol structure in both the radical polymerization and the ionic polymerization is as high as 3 kcal / mol. Therefore, those who preserve the stability of the second-order thiol structure dominate.

-2,4,6(1H,3H,5H)-三酮、三羥甲基丙烷-三(3-巰基丁酸酯)、四(3-巰基丁酸酯)甘脲、四(2-巰基丙酸酯)甘脲、四(2-巰基異丁酸酯)甘脲、四(4-巰基戊酸酯)甘脲等。 Furthermore, from the viewpoints of the hardenability of the hardenable composition and the acid resistance of the hardened product, 1,4-bis (3-mercaptobutyryloxy) butane and pentaerythritol tetrakis (3-mercaptobutane) can be suitably used. Acid ester), 1.3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-tris

-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane-tris (3-mercaptobutyrate), tetra (3-mercaptobutyrate) glycoluril, tetra (2-mercapto) Propionate) glycoluril, tetrakis (2-mercaptoisobutyrate) glycoluril, tetrakis (4-mercaptovalerate) glycoluril, and the like.

The thiol compound (B) may be used alone or in combination of two or more. The molecular weight of the thiol compound (B) is not particularly limited, but from the viewpoint of improving the acid resistance of the cured product of the curable composition of the present embodiment, it is preferably 200 or more and 1,000 or less.

-2,4,6(1H,3H,5H)-三酮(昭和電工股份有限公司製之商品名Karenz MT(商標)NR1)、三羥甲基丙烷三(3-巰基丁酸酯)(昭和電工股份有限公司製之商品名TPMB)等。 The thiol compound (B) is easily available from a commercially available product. Among the second-order thiols containing two or more mercapto groups in one molecule, one which is easy to obtain from commercially available products includes 1,4-bis (3-mercaptobutoxy) butane (Showa Karenz MT (trademark) BD1), Pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz MT (trademark) PE1, Showa Denko Corporation), 1,3,5- Tris (3-mercaptobutyryloxyethyl) -1,3,5-tri

-2,4,6 (1H, 3H, 5H) -trione (trade name Karenz MT (trademark) NR1 manufactured by Showa Denko Corporation), trimethylolpropane tri (3-mercaptobutyrate) (Showa (Trade name: TPMB, manufactured by Denko Corporation).

The preferred content of the thiol compound (B) in the curable composition of the present embodiment is the number of (meth) allyl compounds and thiol compounds that can contain the (meth) allyl compound (A). (B) The ratio of the number of thiol groups is shown. That is, the (meth) allyl-containing compound (A) The ratio of the number of (meth) allyl groups to the number of thiol groups of the thiol compound (B) (the number of allyl groups / the number of thiol groups) is preferably from the viewpoint of hardenability and acid resistance. The range is 0.25 or more and 4 or less, and more preferably 0.6 or more and 4 or less. In such a manner, the content of the (meth) allyl-containing compound (A) and the thiol compound (B) in the curable composition can be determined.

The (meth) allyl number of the (meth) allyl-containing compound (A) means the number of (meth) allyl compounds belonging to the (meth) allyl-containing compound (A). The total number (Mole number) of the number of allyl groups, the so-called number of thiol groups of the thiol compound (B) means the total number (Mole) of the number of thiol groups of all compounds belonging to the thiol compound (B). number).

In addition, as long as it is an amount within a range that does not impair the effect of the invention, a mercapto group-containing compound other than the thiol compound (B) may be added to the curable composition of the present embodiment. However, the blending amount of the mercapto group-containing compound other than the thiol compound (B) is preferably from the viewpoint of maintaining hardenability, acid resistance, and the like, including all the thiol compound-containing compounds. The content is 20% by mass or less.

[3] Compound (C)

The curable composition of this embodiment contains at least one compound (C) selected from an epoxy (meth) acrylate, a (poly) ester (meth) acrylate, and an unsaturated polyester resin.

Epoxy (meth) acrylate means that polyepoxide and (form All of the compounds to which acrylic acid or its anhydride is reacted. The number of (meth) acrylic acid fluorenyl groups (average number of functional groups) of the epoxy (meth) acrylate is preferably 1.5 or more. When the average number of functional groups is 1.5 or more, since the crosslinking density when the curable composition is cured is sufficiently large, the acid resistance of the obtained cured product is good. The epoxy (meth) acrylate may be used alone or in combination of two or more.

The polyepoxide is preferably a compound having an average of 1.5 or more, more preferably an average of 2 or more and 5 or less epoxy groups per molecule. Specific examples of the polyepoxide include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diglycidyl. Ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane Aliphatic polyepoxides such as triglycidyl ether.

In addition, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, hydrogenated bisphenol A type epoxy resin, and hydrogenated bisphenol may also be mentioned. F type epoxy resin, hydrogenated bisphenol S type epoxy resin, hydrogenated bisphenol AD type epoxy resin, tetrabromobisphenol A type epoxy resin and other bisphenol type epoxy resins.

In addition, o-cresol novolac type epoxy resin, phenol novolac type epoxy resin, naphthol novolac type epoxy resin, bisphenol A novolac type epoxy resin, brominated phenol novolac type Epoxy resin, alkylphenol novolac epoxy resin, bisphenol S novolac epoxy resin, methoxyl-containing novolac epoxy resin, brominated benzene Novolac type epoxy resin such as phenol novolac type epoxy resin.

In addition, phenol aralkyl-type epoxy resins (epoxides commonly known as Xyloc resins), diallyl ethers of resorcinol, diallyl ethers of hydroquinones, and children Difunctional epoxy resins of diphenol epoxy resin, biphenyl epoxy resin, tetramethylbiphenyl epoxy resin, etc., or triglycidyl isotricyanate, triphenyl Methane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl modified novolac type epoxy resin (phenol is connected via bismethylene Polyepoxides having a core polyvalent phenol resin), methoxy-containing phenol aralkyl resins, and the like having a structure having an alicyclic structure, an aromatic ring structure, or a heterocyclic structure.

The reaction between the polyepoxide and (meth) acrylic acid or its anhydride is usually carried out at a temperature in the range of 50 ° C to 150 ° C, for about 1 hour to 8 hours. When the polyepoxide is reacted with (meth) acrylic acid or its anhydride, a catalyst is preferably used. Specific examples of the catalyst include amines such as triethylamine, dimethylbutylamine, and tri-n-butylamine, or tetramethylammonium, tetraethylammonium, and benzyltriethylammonium salts. The quaternary ammonium salt. Specific examples of the catalyst include phosphines such as a quaternary phosphonium salt and triphenylphosphine, or imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole.

等共存於反應系中。還有，於此反應時，為了抑制(甲基)丙烯酸的聚合反應，亦可在空氣等的氣流下反應，又，當時為了防止空氣所致的氧化反應，亦可併用2,6-二第三丁基甲基苯酚等之抗氧化劑。 When the polyepoxide is reacted with (meth) acrylic acid or its anhydride, alcohol-based solvents such as methanol, propanol, and ethyl cellosolve, and ester systems such as methylcellosolve acetate can be used. Solvents, ketone solvents such as methyl ethyl ketone, and aromatic compound solvents such as benzene and toluene are used as reaction solvents. In addition, during this reaction, hydroquinone and phenanthrene which are polymerization inhibitors can also be used.

Coexistence in the reaction system. In addition, in this reaction, in order to suppress the polymerization of (meth) acrylic acid, the reaction can also be performed under a stream of air or the like. At the time, in order to prevent the oxidation reaction caused by air, 2,6-second Antioxidants such as tributylmethylphenol.

From the viewpoint of acid resistance and adhesion of the cured product of this embodiment, it is preferable that the epoxy (meth) acrylate is at least one selected from an alicyclic structure, an aromatic ring structure, and a heterocyclic structure. An epoxy (meth) acrylate derived from a structured epoxy compound. In addition, a particularly excellent corrosion resistance to a very strong acid is an epoxy (meth) acrylate derived from an epoxy compound having a bisphenol A type skeleton.

Among the epoxy (meth) acrylates having a bisphenol A type skeleton, as commercially available products, Epoxy Ester 3002M (N) and Epoxy Ester manufactured by Kyoeisha Chemical Co., Ltd. can be cited. 3002A (N), Epoxy Ester 3000MK, Epoxy Ester 3000A, or NK Ester EA-1020, NK Ester A-B126PE, NK Ester ABE-300, NK Ester A-BPE-4, NK Ester A-BPE-500, NK Oligo EA-5220, or VR-77 manufactured by Showa Denko Corporation.

Next, the (poly) ester (meth) acrylate means a saturated or unsaturated polyester having at least one (meth) acrylfluorene group in one molecule. This (poly) ester (meth) acrylate is obtained by reacting a diol (if necessary, a triol) with an ester of a dibasic acid or its anhydride (if necessary, a tribasic acid or its anhydride). At that time, it was also possible to use a single epoxy compound or a polyepoxide 组合。 The compound. Moreover, (poly) ester (meth) acrylate type may be used individually by 1 type, and may use 2 or more types together.

Examples of the diol as a raw material of polyester include 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, Aliphatic diols represented by 1,10-decanediol, etc., or hydrogenated dimer diols (e.g., carbon number 36 or 44), 1,4-cyclohexanedimethanol, 1,3-adamantine Alicyclic diols represented by alkanediol, tricyclodecanedimethanol, or ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexanediol, dimethylolcyclohexane, 2 Alkanediols represented by 2,2,4-trimethyl-1,3-pentanediol, etc., or represented by diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, etc. The polyalkylene glycols. In addition, the addition of divalent phenols represented by bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, etc., and alkylene oxides represented by ethylene oxide and propylene oxide can also be cited. Reaction products.

Examples of the triol used as a raw material of the polyester include glycerol, trimethylolethane, 1,2,6-hexanetriol, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, 1, 3,5-adamantanetriol, 1,3,5-cyclohexanetriol, trimer triol (e.g., carbon number 54), and the like. Examples of the triol having a heterocyclic ring include tris (2-hydroxyethyl) isotricyanate, tris (3-hydroxypropyl) isotricyanate, and tris (4-hydroxybutane). Group) isocyanurate and the like.

Examples of the tetraol used as a raw material of the polyester include pentaerythritol, diglycerol, 1,2,3,4-butane tetraol, and the like. As a single epoxy compound, Examples thereof include ethylene oxide, propylene oxide, epichlorohydrin, styrene oxide, and phenylglycidyl ether. Examples of the polyepoxy compound include epoxy resins described in the "General Epoxy Resin" edited by the Epoxy Resin Technology Association.

Examples of the dibasic acid and its anhydride used as raw materials of polyester include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, 1 Aliphatic or alicyclic saturated dibasic acids, 1,2-dodecanoic acid, and esters thereof, or maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid Α, β-unsaturated dibasic acids and their anhydrides of acids, and their esters.

In addition, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrachlorophthalic acid, tetrahydrophthalic anhydride, and Aromatic diacids of bromophthalic acid, internal methylenetetrahydrophthalic acid, halogenated phthalic anhydride, and esters thereof, and their anhydrides.

Examples of the tribasic acid and its anhydride as polyester raw materials include trimellitic acid, aconitic acid, butanetricarboxylic acid, and 6-carboxy-3-methyl-1,2,3,6- Hexahydrophthalic acid and its anhydride. Examples of the tetrabasic acid and its anhydride include pyromellitic acid and butanetetracarboxylic acid and its anhydride.

As a method for producing a (poly) ester (meth) acrylic acid ester, a diol (an alcohol having a trivalent or higher valency as required) and a (meth) acrylic acid and a dibasic acid (optionally having a trivalent or higher valence as required) are generally used. Acid). However, it is also possible to use a compound having a (meth) acrylfluorenyl group and a hydroxyl group and a dibasic acid (a polyvalent acid having a trivalent or higher valence if necessary). Method of esterification.

From the viewpoint of acid resistance and adhesion of the cured product, a (poly) ester (meth) acrylate having at least one structure selected from an alicyclic structure, an aromatic ring structure, and a heterocyclic structure is preferred, More preferred is a (poly) ester (meth) acrylate derived from bisphenol A. As a (poly) ester (meth) acrylate having a bisphenol A type skeleton that can be obtained from a commercially available product, Ebecry 1812 manufactured by Daicel-Allnex Corporation represented by the following formula (9) is mentioned. In addition, R ¹⁹ in Formula (9) represents a hydrogen atom or a methyl group, and R ²⁰ and / or R ²¹ represents a group having a bisphenol A type skeleton.

Next, the unsaturated polyester resin is an unsaturated polyester (prepolymer) obtained by polycondensing an acid component formed from an α, β-unsaturated dibasic acid or an anhydride thereof with a polyol.

The production method of the unsaturated polyester resin is not particularly limited, and examples thereof include a method of performing a polycondensation reaction of a polybasic acid component and a polyhydric alcohol component. This polycondensation reaction is a condensation water generated when the two components are reacted Remove to the outside of the system. The unsaturated polyester resin also includes a (meth) acrylate obtained by reacting an epoxy compound containing an α, β-unsaturated carboxylic acid ester group with a terminal carboxyl group of the unsaturated polyester resin. The hydroxyl-containing (meth) acrylate and the unsaturated polyester resin A (meth) acrylate obtained by reacting a terminal carboxyl group and a (meth) acrylate obtained by reacting (meth) acrylic acid with a terminal hydroxyl group of the unsaturated polyester resin. The unsaturated epoxy resins may be used alone or in combination of two or more.

From the viewpoint of acid resistance of the cured product, the unsaturated polyester resin preferably has at least one structure selected from an alicyclic structure, an aromatic ring structure, and a heterocyclic structure, and more preferably has a bisphenol A type skeleton. If it has a bisphenol A-type skeleton, in addition to acid resistance, it also provides heat resistance or toughness to a hardened material, and therefore has excellent practicality when used as an industrial product. Examples of commercially available unsaturated polyester resins having a bisphenol A-type skeleton include Rigolac LP-1M manufactured by Showa Denko Corporation. This Rigolac LP-1M is a polymer represented by the following formula (10) and / or a polymer represented by the following formula (11). In addition, R ²² and R ^{23 in} Formula (10) and Formula (11) represent a group having a bisphenol A type skeleton.

The molecular weight of the compound (C) is not particularly limited, but From the viewpoint of improving the acid resistance of the cured product of this embodiment, it is preferably 400 or more.

In addition, regarding the preferable content of the compound (C) in the curable composition of the present embodiment, the (meth) allyl-containing compound (A) and a thiol are included from the viewpoint of acid resistance of the cured product. When the total content of the compound (B) and the compound (C) is taken as 100 parts by mass, the content of the compound (C) therein is preferably set to 10 parts by mass or more and 80 parts by mass or less, more preferably 10 parts by mass or more and 70 It is particularly preferably 30 parts by mass or more and 70 parts by mass or less.

[4] Polymerization initiator (D)

The polymerization initiator (D) includes a photopolymerization initiator and a thermal polymerization initiator, and any compound can be used as long as it can promote the start of polymerization of the (meth) allyl-containing compound (A). The polymerization initiator (D) may be used singly or in combination of two or more kinds in any ratio.

The type of the photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals that contribute to the start of radical polymerization by irradiation with active energy rays such as near infrared rays, visible rays, and ultraviolet rays.

Examples of the photopolymerization initiator include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, and 1 2,2-hydroxy-2-methyl-1-phenylpropane-1-one, α-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylacetone, 2-hydroxy-2- Methyl-1- (4-isopropylphenyl) acetone, 2-hydroxy-2-methyl-1- (4-dodecylbenzene ) Acetone, 2-hydroxy-2-methyl-1-[(2-hydroxyethoxy) phenyl] acetone, diphenyl ketone, 2-methyldiphenyl ketone, 3-methyldiphenyl Ketone, 4-methyldiphenyl ketone, 4-methoxydiphenyl ketone, 2-chlorodiphenyl ketone, 4-chlorodiphenyl ketone, 4-bromodiphenyl ketone, 2-carboxydiphenyl Ketone, 2-ethoxycarbonyldiphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide, diphenylketone tetracarboxylic acid or its tetramethyl ester, 4,4'- Bis (dialkylamino) diphenyl ketones (e.g. 4,4'-bis (dimethylamino) diphenyl ketone, 4,4'-bis (dicyclohexylamino) diphenyl ketone , 4,4'-bis (diethylamino) diphenyl ketone, 4,4'-bis (dihydroxyethylamino) diphenyl ketone), 4-methoxy-4'-dimethyl Aminodiphenyl ketone, 4,4'-dimethoxydiphenyl ketone, 4-dimethylaminodiphenyl ketone, 4-dimethylaminoacetophenone, diphenylethylene Ketone, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, phenanthrenequinone, fluorenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Methyl ethyl ketone, 2-methyl-1- [4- (a ) Phenyl] -2-morpholino-1-acetone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzene Paraffin ethers (e.g. benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin phenyl ether, Benzyldimethylketal), acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, 2,4,6- Trimethylbenzylidene diphenylphosphine oxide, 2,6-dimethoxybenzylidene diphenylphosphine oxide, 2,6-dichlorobenzylidene diphenylphosphine oxide, 2,4,6-trimethylbenzylfluorenylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzylfluorenylethoxyphenylphosphine oxide, 2,3,5, 6-tetramethylbenzylidene diphenylphosphine Oxide, benzamidine bis (2,6-dimethylphenyl) phosphonate, 1- [4- (phenylthio) phenyl] -1,2-octanedione-2- (O- Benzamidine oxime), 1- [9-ethyl-6- (2-methylbenzylhydrazine) -9H-carbazol-3-yl] ethanone-1- (O-acetamyl oxime) , 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -3-cyclopentylacetone-1- (O-acetamidooxime), 1- [4- (phenylthio) phenyl] -3-cyclopentylpropane-1,2-dione-2- (O-benzylideneoxime), bis- (2,6-dichlorobenzene Formamyl) phenylphosphine oxide, bis- (2,6-dichlorobenzyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzyl) Phenyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzyl) Phenyl) phosphine oxide, bis- (2,6-dimethoxybenzyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxy Phenylbenzyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzyl) phenylphosphine oxide, (2,5,6- Trimethylbenzyl) -2,4,4-trimethylpentylphosphine oxide, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthio Tonone, 2,4-dichlorothioxanthone , 1-chloro-4-propoxythioxanthone, etc.

As the photopolymerization initiator, a metallocene compound can also be used. As the metallocene compound, a metallocene compound having a central metal such as Fe, Ti, V, Cr, Mn, Co, Ni, Mo, Ru, Rh, Lu, Ta, W, Os, Ir, etc. can be used. Examples thereof include bis (η5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (pyrrole-1-yl) phenyl] titanium.

In particular, from the viewpoint of the stability of the curable composition after the photopolymerization initiator is added, it is preferable to use the photopolymerization initiator as the photopolymerization initiator. With 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 2,4,6-trimethyldiphenyl ketone, 4-methyldiphenyl Ketone, ethoxyphenyl (2,4,6-trimethylbenzyl) phosphine oxide and 2-hydroxy-2-methylphenylacetone.

1-Hydroxycyclohexylphenyl ketones are available under the product name of Irgacure 184 from BASF, and 2,4,6-trimethylbenzylidene diphenylphosphine oxides are available under the product name of LUCIRIN TPO. Acquired by the company. In addition, the ethoxyphenyl (2,4,6-trimethylbenzyl) phosphine oxide is available under the product name of Irgacure TPO-L from BASF, and 2-hydroxy-2-methyl Phenylacetone is available under the product name of Darocur 1173 from BASF.

Particularly preferred photopolymerization initiators include diphenyl-2,4,6-trimethylbenzylidenephosphine oxide, 2-hydroxy-2-methylphenylacetone, and 2-hydroxy-1 -(4-isopropenylphenyl) -2-methylpropane-1-one and its oligomers, 2,4,6-trimethyldiphenyl ketone, and LAMBERTI which is a mixture of these The product name manufactured by SpA is "ESACURE KTO 46".

The thermal polymerization initiator is not particularly limited as long as it does not adversely affect physical properties such as acid resistance of the cured product, and a known one can be used. The thermal polymerization initiator used in this embodiment is preferably one which is soluble in other components present in the hardenable composition to be hardened and generates radicals at a temperature of 30 ° C. to 120 ° C.

Specific examples of the thermal polymerization initiator include diisopropylperoxydicarbonate, dicyclohexylperoxydicarbonate, and di-n-propylperoxy. Organic peroxides such as dicarbonate, disecond butyl peroxydicarbonate, third butyl perbenzoate, and the like are not limited thereto. However, from the viewpoint of the curability of the curable composition of the present embodiment, diisopropylperoxydicarbonate is preferred.

Examples of the peroxide-based polymerization initiator include dibenzofluorenyl peroxide, third butyl permaleate, di-t, t-hexyl peroxide, and third hexyl group. Peroxy-2-ethylhexanoate, third butyl hydroperoxide, and the like. Examples of the redox polymerization initiator include a combination of persulfate and sodium bisulfite, a combination of peroxide and sodium ascorbate, and the like. On the other hand, examples of the persulfate include potassium persulfate and ammonium persulfate.

The content of the polymerization initiator (D) in the curable composition of the present embodiment is, from the viewpoint of the curability of the curable composition, the polymerizable initiator (D) is subtracted from the entire amount of the curable composition. ) And non-reactive solvents, inorganic fillers, and other non-reactive components, such as (meth) allyl-containing compound (A) and thiol compound (B) and compound (C) The total content is regarded as the content of the polymerization initiator (D) when 100 parts by mass, and is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.5 parts by mass or more and 5.0 parts by mass or less.

[5] Polymerization inhibitor

The curable composition of this embodiment may contain a polymerization inhibitor as needed in order to suppress the radical polymerization during storage and improve storage stability. The type of the polymerization inhibitor is not particularly limited, and examples thereof include 4-methoxy -1-naphthol, 1,4-dimethoxynaphthalene, 1,4-dihydroxynaphthalene, 4-methoxy-2-methyl-1-naphthol, 4-methoxy-3-methyl 1-naphthol, 1,4-dimethoxy-2-methylnaphthalene, 1,2-dihydroxynaphthalene, 1,2-dihydroxy-4-methoxynaphthalene, 1,3-dihydroxy- 4-methoxynaphthalene, 1,4-dihydroxy-2-methoxynaphthalene, 1,4-dimethoxy-2-naphthol, 1,4-dihydroxy-2-methylnaphthalene, pyrofluorene Phenol, methylhydroquinone, third butylhydroquinone, 4-methoxyphenol, N-nitroso-n-phenylhydroxylamine, and the like.

Among these, methyl hydroquinone, pyrogallol, and tertiary butyl hydroquinone are preferable from the viewpoint of the storability of the curable composition.

These polymerization inhibitors may be used singly or in combination of two or more kinds.

The content of the polymerization inhibitor in the curable composition of the present embodiment is not particularly limited, but from the viewpoint of storage stability of the curable composition, the (meth) allyl-containing compound (A) When the total content of the thiol compound (B) is taken as 100 parts by mass, the content of the polymerization inhibitor is preferably less than 0.1 part by mass, more preferably 0.0001 part by mass or more and 0.05 part by mass or less.

[6] Other ingredients that can be added to the curable composition

The curable composition system of the present embodiment may contain (meth) allyl-containing compound (A), thiol compound (B), compound (C), and polymerization initiator (D). The polymerization inhibitor of a component may contain other components within the range which does not impair the objective of this invention.

In addition, the curable composition of this embodiment is The other components may be solvent-free or solvent-containing, but it is preferably solvent-free.

Those that are preferably contained as other components include, for example, carbon materials, color materials such as pigments and dyes, and inorganic fillers.

Examples of the carbon material include carbon black, acetylene black, lamp black, and graphite.

Examples of the pigment include black pigments such as iron black, aniline black, cyanine black, and titanium black.

Moreover, the curable composition of this embodiment may contain organic pigments, such as red, green, and blue. For example, a commercially available nail cream or a UV process pigment can be used. Examples of such pigments include Pika-Ace coloring pigments (701, 731, 741, 755, 762) and transparent pigments (900, 901, 910, 920, 921, 922, 924, 930, 932, 941, 942) , 945, 947, 950, 955, 957, 960, 963, 968, 970, 980, 981, 982, 985) and so on.

Examples of the dye include direct dyes, acid dyes, basic dyes, mordant dyes, acid mordant dyes, vat dyes, disperse dyes, reactive dyes, fluorescent whitening dyes, and plastic dyes. The dye means a substance having solubility in a solvent or compatibility with a resin, and having a property of coloring a dissolved or compatible substance.

The color material can be used alone or in combination of two or more.

The content of the coloring material in the curable composition of this embodiment is not particularly limited, but if the concentration is too high, the transmittance of the active energy ray decreases. Low, there is a possibility that the hardening composition may fail to harden. Therefore, the content of the color material in the curable composition is preferably 0.0001% by mass or more and 40% by mass or less.

The inorganic filler is not particularly limited as long as it can be dispersed in the (meth) allyl-containing compound (A), thiol compound (B), and compound (C) to form a paste. As such an inorganic filler, for example, silicon dioxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), titanium oxide (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), Silicon nitride (Si ₃ N ₄ ), barium titanate (BaO‧TiO ₂ ), barium carbonate (BaCO ₃ ), lead titanate (PbO‧TiO ₂ ), lead zirconate titanate (PZT), zirconate titanate Lead lanthanum (PLZT), gallium oxide (Ga ₂ O ₃ ), spinel (MgO‧Al ₂ O ₃ ), mullite (3Al ₂ O ₃ ‧ 2SiO ₂ ), vermiculite (2MgO‧2Al ₂ O ₃ / 5SiO ₂ ), talc (3MgO‧4SiO ₂ ‧H ₂ O), aluminum titanate (TiO ₂ -Al ₂ O ₃ ), yttria-containing zirconia (Y ₂ O ₃ -ZrO ₂ ), barium silicate (BaO ‧8SiO ₂ ), boron nitride (BN), calcium carbonate (CaCO ₃ ), calcium sulfate (CaSO ₄ ), zinc oxide (ZnO), magnesium titanate (MgO‧TiO ₂ ), barium sulfate (BaSO ₄ ), organic Fiber reinforced materials such as bentonite, carbon (C), glass powder, synthetic mica, boron nitride fiber, etc., are mixed with an inorganic support to make them powdery. Polysiloxane resin or polysiloxane Powdered rubber. These inorganic fillers may be used singly or in combination of two or more kinds.

Among the inorganic fillers exemplified above, the viscosity adjustability of the curable composition of the present embodiment and the curability of the curable composition of the present embodiment From the viewpoint of sheet formability of the hardened product formed from the composition, fine particle silicon dioxide is preferred. Microparticle silica is available under the trade name Aerosil (trademark) from Japan Aerosil Corporation.

Aerosil (trademark) trade name for fine particle silica includes Aerosil (trademark) OX50, RX50, RY50, 50, NAX50, NY50, NA50H, NA50Y, 90G, NX90G, 130, R972, RY200S, 150, R202 , 200, R974, R9200, RX200, R8200, RY200, R104, RA200H, RA200HS, NA200Y, R805, R711, R7200, 300, R976, R976S, RX300, R812, R812S, RY300, R106, 380, P25, T805, P90 , NKT90, AluC, AluC805 and so on. Among these fine particles of silica, RX200 is more preferable from the viewpoint of dispersibility.

The content of the inorganic filler in the curable composition of the present embodiment is not particularly limited, but from the viewpoint of moldability of the cured product formed from the curable composition of the present embodiment, it will contain (methyl) Allyl compound (A), thiol compound (B) and at least one compound selected from epoxy (meth) acrylate, (poly) ester (meth) acrylate, and unsaturated polyester resin ( When the total content of C) is taken as 100 parts by mass, the content of the inorganic filler is preferably less than 10 parts by mass, and more preferably 2 parts by mass or more and 6 parts by mass or less.

The curable composition of the present embodiment may contain, in addition to the color material, the following (a) to (w) as other components. These other components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

(a) Thermoplastic resin

(b) Deodorant

(c) Adhesive improvers such as silane coupling agents and titanium coupling agents

(d) Antioxidants such as hindered amines, hydroquinones, hindered phenols, etc.

(e) UV absorbers such as diphenyl ketones, benzotriazoles, salicylates, and metal salts

(f) Stabilizers for metal soaps, inorganic or organic salts of heavy metals (e.g. zinc, tin, lead, cadmium), organic tin compounds, etc.

(g) pH adjusters for aliphatic carboxylic acids such as acetic acid, acrylic acid, palmitic acid, oleic acid, and mercaptocarboxylic acids, or aromatic organic acids such as phenol, naphthol, benzoic acid, and salicylic acid

(h) Plasticizers of phthalates, phosphates, fatty acid esters, epoxidized soybean oil, castor oil, flowing paraffin, alkyl polycyclic aromatic hydrocarbons, etc.

(i) Waxes such as paraffin, microcrystalline wax, polymeric wax, beeswax, whale wax, low molecular weight polyolefin, etc.

(j) Non-reactive diluent for benzyl alcohol, tar, asphalt, etc.

(k) Fillers for acrylic resin powder, phenol resin powder, etc.

(I) Solvents of ethyl acetate, toluene, alcohols, ethers, ketones, etc.

(m) Foaming agent

(n) Dehydrating agents such as silane coupling agents, monoisocyanate compounds, and carbodiimide compounds

(o) Antistatic agent

(p) Antibacterial agents

(q) Fungicide

(r) Viscosity modifier

(s) spice

(t) Flame retardant

(u) Leveling agent

(v) Sensitizer

(w) Dispersant

[7] Preparation of hardening composition

The curable composition of the present embodiment can be appropriately mixed with a (meth) allyl-containing compound (A), a thiol compound (B), a compound (C), and a polymerization initiator (D) together with polymerization as required. Inhibitors and other ingredients.

In this case, the ratio of the number of (meth) allyl groups of the compound (A) which may contain (meth) allyl group to the number of thiol groups of the thiol compound (B) (number of allyl groups / number of thiol groups) The number) is mixed so as to fall within a range of 0.25 or more and 4 or less (more preferably 0.6 or more and 4 or less).

When the total content of the (meth) allyl-containing compound (A), the thiol compound (B), and the compound (C) is taken as 100 parts by mass, the content of the compound (C) may be 10 parts by mass. 80 mass parts or less (more preferably 10 mass parts or more and 70 mass parts or less, and more preferably 30 mass parts or more and 70 mass parts or less), mixing is performed.

In addition, the amount after deducting the content of the polymerizable initiator (D) from the entire amount of the curable composition can be regarded as a polymerization initiator at 100 parts by mass. The content of (D) is within a range of 0.01 parts by mass or more and 10 parts by mass or less (more preferably 0.5 parts by mass or more and 5.0 parts by mass or less), and mixed.

The method for preparing the curable composition of this embodiment is not particularly limited, and may be a compound (A), a thiol compound (B), a compound (C), or a polymerization initiator using (meth) allyl (D) A method of mixing and dispersing the raw materials of the curable composition, including the lead. Examples of the method of mixing and dispersing include the following methods.

(Ii) Put each raw material into a container such as a glass beaker, a can, a plastic cup, an aluminum cup, and knead with a stirring rod, a spatula, or the like.

(Ii) Each raw material is kneaded by a double spiral stirring blade, a gate blade, and the like.

(Ii) Each material is kneaded by a planetary mixer.

(Ii) Each raw material is kneaded by a bead mill.

(Ii) Each raw material is kneaded by a three-roller.

(Ii) Each material is kneaded by an extrusion type kneading extruder.

(ㄋ) Each material is kneaded by a rotation and revolution mixer.

The addition and mixing of each raw material may be performed in an arbitrary order, and all raw materials may be added simultaneously or sequentially.

When the polymerization initiator (D) is used, it is illuminated by an active energy ray after passing through a filter capable of removing light of absorption wavelength decomposed by the photopolymerization initiator, or the active energy ray is not irradiated, or the thermal polymerization is initiated. The curing agent is processed at a temperature lower than the curing temperature, and before the curing treatment, under the condition that the polymerization initiator (D) is not activated, a pre-curing treatment such as the operation and mixing of the above-mentioned raw materials is performed.

[8] Method for hardening hardening composition

The hardenable composition of this embodiment is irradiated with active energy rays or heated to harden the hardenable composition to obtain a hardened material. Examples of the active energy rays used at the time of curing include ultraviolet rays, electron rays, and X-rays. In terms of being able to use inexpensive devices, ultraviolet rays are preferred.

As the light source when the curable composition of this embodiment is cured by ultraviolet rays, various ones can be used. Examples include black light, UV-LED lamps, high-pressure mercury lamps, pressurized mercury lamps, metal halide lamps, xenon lamps, and electrodeless discharge lamps.

The so-called black light here is the special ultraviolet light emitting phosphor that can cut off visible light and ultraviolet light with a wavelength below 300 nm. It emits only near-ultraviolet light with a wavelength of 300 nm to 430 nm (around 350 nm). light. The so-called UV-LED lamp is a lamp using a light-emitting diode capable of emitting ultraviolet rays. Among these light sources, from the viewpoint of hardenability, metal halide lamps, high-pressure mercury lamps, and LED lamps (UV-LED lamps) are preferred.

The amount of irradiation of the active energy rays may be a sufficient amount to harden the hardenable composition of this embodiment, and it may be in accordance with the composition, usage amount, thickness, and shape of the hardened composition of the hardenable composition of this embodiment. Wait to choose. For example, for a coating film formed by applying the curable composition of this embodiment, when irradiating ultraviolet rays, an exposure amount of 200 mJ / cm ^{2 to} 5000 mJ / cm ² is preferably used, and more preferably 1000 mJ / cm ² Above 3000mJ / cm ² exposure. The above exposure amount is a value when the measurement wavelength is 365 nm.

The coating (coating) method for applying the curable composition of the present embodiment to a substrate, for example, to form a coating film is not particularly limited. For example, in addition to the spray method or the dipping method, a natural coater, a curtain coater, a notch wheel coater, a gravure coater, a microgravure coater, and a die coater can be used. Machine, curtain coater, contact roll, squeeze roll, reverse roll, air knife, scraper belt type applicator, floating knife, roll liner scraper, pad liner scraper, etc.

By processing the hardenable composition of this embodiment into a sheet shape and curing it, a sheet-shaped hardened material, that is, a sheet material can be obtained. This sheet material may contain other components other than the hardened | cured material of the hardenable composition of this embodiment as needed.

The thickness of the sheet material can be appropriately set according to the application, but it is preferably from 0.1 mm to 10 mm, and from the viewpoint of moldability, more preferably from 0.3 mm to 8 mm.

It should be noted that this embodiment shows an example of the present invention, and the present invention is not limited to this embodiment. In addition, various changes or improvements can be added to this embodiment, and the forms added with such changes or improvements can also be included in the present invention.

[Example]

Examples and comparative examples are shown below to explain the present invention in more detail. Various materials such as (meth) allyl-containing compound (A), thiol compound (B), compound (C), and polymerization initiator (D) These were mixed to prepare the curable compositions of Examples 1 to 16 and Comparative Examples 1 to 4. Hereinafter, various raw materials used in the preparation of the curable composition will be described.

(i) Compound (A) containing (meth) allyl

As the (meth) allyl-containing compound (A), the following four compounds (i-1) to (i-4) were used.

(i-1) SR-25 (quantity) manufactured by Showa Denko Corporation as a mixture of an allyl-containing compound represented by the following formula (12) and an allyl-containing compound represented by the following formula (13) Average molecular weight 355354 (measured in accordance with JIS K 0070 method, the number of iodine valence, converted into the number average molecular weight value), the number of allyl groups 2, allyl equivalent 177)

The mixing ratio of the allyl-containing compound represented by the formula (12) and the allyl-containing compound represented by the formula (13) was 6: 4. In addition, t and u in Formula (12) and Formula (13) are each independently an integer of 1 or more and 3 or less.

(i-2) diallyl 1,4-cyclohexanedicarboxylic acid (trade name H-DATP, manufactured by Showa Denko Corporation, molecular weight 252, number of allyl groups 2, allyl equivalent 126)

(i-3) Bisphenol A diallyl ether (trade name CM-BPAED manufactured by Chembridge, molecular weight 308, number of allyl groups 2, allyl equivalent 154)

(i-4) Diethylene glycol bis (allyl carbonate) (trade name RAV7-AT manufactured by Mitsui Chemicals, Inc., molecular weight 274, number of allyl groups 2, allyl equivalent 137)

(ii) Thiol compound (B)

As the thiol compound (B), the following three compounds (ii-1) to (ii-3) were used.

(ii-1) Pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz MT (trademark) PE1, manufactured by Showa Denko Corporation, molecular weight 545, number of mercapto groups 4, mercapto equivalent 136)

-2,4,6(1H,3H,5H)-三酮(昭和電工股份有限公司製之商品名Karenz MT(商標)NR1，分子量568，巰基之數3，巰基當量189) (ii-2) 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-tris

-2,4,6 (1H, 3H, 5H) -trione (Karnz MT (trademark) NR1 manufactured by Showa Denko Corporation, molecular weight 568, number of mercapto groups 3, mercapto equivalent 189)

(ii-3) Pentaerythritol tetrakis (3-mercaptopropionate) (trade name PEMP manufactured by Sakai Chemical Industry Co., Ltd., molecular weight 489, number of mercapto groups 4, mercapto equivalent 122)

(iii) Compound (C)

As the compound (C), the following four compounds (iii-1) to (iii-4) were used.

(iii-1) Epoxy acrylate having a bisphenol A type skeleton (VR77 manufactured by Showa Denko Corporation)

(iii-2) Polyester acrylate having a bisphenol A type skeleton (Ebecryl 812 manufactured by Daicel-Allnex Co., Ltd.)

(iii-3) Unsaturated polyester resin having a bisphenol A type skeleton (trade name Rigolac LP-1M manufactured by Showa Denko Corporation)

(iii-4) An epoxy acrylate represented by the following formula (14) (trade name Epoxy Ester 70PA manufactured by Kyoeisha Chemical Co., Ltd.)

(iv) Compound (c) containing (meth) acryloxy groups other than compound (C)

As the compound (c) containing a (meth) acryloxy group other than the compound (C), trimethylolpropane triacrylate (trade name Light Acrylate TMP-A manufactured by Kyoeisha Chemical Co., Ltd. was used, and molecular weight was used. 296, the number of propylene methoxy groups 3).

(v) Polymerization initiator (D)

As the polymerization initiator (D), ESACURE KTO46 manufactured by DKSH Japan Co., Ltd. was used.

A (meth) allyl-containing compound (A), a thiol compound (B), a compound (C), and / or a (meth) acryloxy group-containing compound (c) and a polymerization initiator (D ) Were mixed at the mass ratios shown in Tables 1 and 2 to prepare a curable composition. In Tables 1 and 2, the "(A) / (B) functional group ratio" indicates the number of (meth) allyl groups of the (meth) allyl-containing compound (A) relative to the thiol compound (B ) Is the ratio of the number of thiol groups (the number of allyl groups / the number of thiol groups).

In Tables 1 and 2, the "mass ratio of (C)" means that the compound (A) containing a (meth) allyl group and the thiol compound (B) with the compound (C) and / or a (methyl group) ) When the total content of the compound (c) of acryloxy group is regarded as 1, the content of the compound (C) and / or the compound (c) containing (meth) acryloxy group is contained therein.

Next, the softness | flexibility, adhesiveness, and acid resistance of the hardened | cured material of the hardenable composition of Examples 1-16 and Comparative Examples 1-4 were evaluated as follows. The results are shown in Tables 1 and 2.

<Evaluation of softness and adhesion>

On a half surface of a copper / polyimide laminated substrate (S'PERFLEX manufactured by Sumitomo Metal Mining Co., Ltd.), a hardening composition was coated with a bar coater into a film shape having a thickness of 50 μm. Then, the film of the curable composition was cured by using a conveyor-type UV irradiation machine ECS-4011GX (high-pressure mercury lamp) manufactured by EYEGRAPHICS Co., Ltd. and irradiated with UV light having an exposure amount of ² J / cm ² to obtain a test sheet. . The obtained test sheet was subjected to a bending resistance test in accordance with JIS K 5600 using a mandrel having a diameter of 2 mm. The flexibility and adhesion were evaluated on three levels of A, B, and C in accordance with the following evaluation criteria.

A: The bending of the test sheet is easy, and the flexibility of the hardened material and the adhesion of the hardened material to the copper / polyimide laminated substrate (the object to be coated) are very excellent.

B: The test sheet can be bent, and the flexibility of the cured product and the adhesion of the cured product to the copper / polyimide laminated substrate are good. However, there are appearance changes such as whitening on the hardened material.

C: The test sheet was broken, and the cured product was peeled from the copper / polyimide laminated substrate. Therefore, the flexibility of the cured product and the adhesion of the cured product to the copper / polyimide laminated substrate are insufficient.

<Evaluation of acid resistance 1>

The test sheet similar to the above was immersed in a sulfuric acid aqueous solution having a concentration of 20% by mass and a temperature of 65 ° C for 30 minutes. The acid resistance 1 of the cured product was evaluated on three levels of A, B, and C according to the following evaluation criteria.

A: The appearance and hardness of the cured product of the curable composition are not changed.

B: The appearance of the cured product of the curable composition is hardly changed, but the cured product is softened and easily peeled from the copper / polyimide laminate substrate.

C: The appearance of the cured product of the curable composition is changed, or the cured product is peeled from the copper / polyimide laminate substrate.

<Evaluation of acid resistance 2>

The test sheet similar to the above was immersed in a sulfuric acid aqueous solution having a concentration of 5% by mass, washed, and then immersed in an electroless tin plating solution 580M12Z manufactured by Ishihara Chemical Co., Ltd. at 60 ° C for 4 minutes. The test sheet was taken out from the electroless tin plating solution, washed with warm water, and then subjected to a eutectic treatment at 120 ° C. for 90 minutes in a blower constant temperature dryer. The acid resistance 2 of the cured product was evaluated on three levels of A, B, and C according to the following evaluation criteria.

A: The copper system of the part covered with the hardened material of the hardenable composition has no discoloration, and can be plated on the uncoated part of the copper-clad / polyimide laminate substrate.

B: The copper / polyimide laminated substrate can be plated on the uncured part, but the appearance of the copper or cured part of the cured part is changed.

C: The appearance of the cured product of the curable composition is changed, or the cured product cannot be plated because the cured product is peeled from the copper / polyimide laminate substrate.

As is clear from the results shown in Tables 1 and 2, since the hardened composition of the hardenable composition of Examples 1 to 16 contains a (meth) allyl-containing compound (A) and a thiol compound ( B), the compound (C) and the polymerization initiator (D), which are excellent in flexibility, adhesion and acid resistance. In particular, when the (meth) allyl-containing compound (A) or thiol compound (B) is a compound having a bisphenol A type skeleton, the acid resistance (especially the result of the acid resistance evaluation 2) is excellent. .

In contrast, the cured product of the curable composition of Comparative Example 1 does not contain the compound (C) because the curable composition does not contain the compound (C). Although it is excellent in flexibility and adhesion, it is inferior in acid resistance. The properties (acid resistance evaluation 2) were poor.

Moreover, since the hardened | cured material of the hardenable composition of the comparative example 2 does not contain a thiol compound (B), it is inferior in adhesiveness, and is also inferior in acid resistance.

Moreover, since the hardened | cured material of the hardenable composition of the comparative example 3 does not contain the (meth) allyl-containing compound (A) and a thiol compound (B), the hardened | cured material is too hard, and adhesiveness is bad. Therefore, when the acid resistance was evaluated, the cured product was peeled from the copper / polyimide laminated substrate, and the evaluation of the acid resistance itself could not be completed.

In addition, the cured product of the curable composition of Comparative Example 4 is the same as that of Comparative Example 3 by using a compound (c) containing a (meth) acryloxy group other than the compound (C) instead of the compound (C). The situation is the same.

Claims (11)

A curable composition comprising a (meth) allyl-containing compound (A) having two or more (meth) allyl groups in one molecule, and a compound having two or more (meth) allyl groups in one molecule Mercapto thiol compound (B), and at least one compound (C) selected from epoxy (meth) acrylate, (poly) ester (meth) acrylate and unsaturated polyester resin, and polymerization Starter (D). The curable composition according to claim 1, wherein the (meth) allyl-containing compound (A) includes a compound having at least one structure selected from an alicyclic structure, an aromatic ring structure, and a heterocyclic structure. The curable composition according to claim 1, wherein the (meth) allyl-containing compound (A) includes a compound having a bisphenol A type skeleton. The curable composition according to claim 1, wherein the (meth) allyl-containing compound (A) includes a compound having at least one of an allyloxycarbonyl group and an N-allyl group. The hardening composition according to any one of claims 1 to 4, wherein The thiol compound (B) includes a compound having two or more thiol groups in one molecule and all of the thiol groups are bonded to a secondary carbon atom or a tertiary carbon atom. The curable composition according to any one of claims 1 to 4, wherein the thiol compound (B) includes a compound having a group represented by the following formula (1); however, R ¹ in the following formula (1) Represents an alkyl group having 1 to 10 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m represents an integer of 0 to 2;

The hardenable composition according to any one of claims 1 to 4, wherein the thiol compound (B) includes 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutane Acid ester), 1,3,5-tris (3-mercaptobutoxyethyl) -1,3,5-tris

-2,4,6 (1H, 3H, 5H) -trione and at least one selected from trimethylolpropane tris (3-mercaptobutyrate). The curable composition according to any one of claims 1 to 7, wherein the compound (C) includes a compound having at least one structure selected from an alicyclic structure, an aromatic ring structure, and a heterocyclic structure. The curable composition according to any one of claims 1 to 7, wherein the compound (C) includes a compound having a bisphenol A type skeleton. The curable composition according to any one of claims 1 to 9, wherein the number of the (meth) allyl groups of the (meth) allyl-containing compound (A) is relative to the thiol compound (B) The ratio of the number of thiol groups (the number of allyl groups / the number of thiol groups) is in the range of 0.25 or more and 4 or less. The (meth) allyl-containing compound (A) and the thiol compound (B) When the total content of the compound (C) is 100 parts by mass, the content of the compound (C) is 10 parts by mass or more and 70 parts by mass or less, and the content of the polymerization initiator (D) is 0.01 part by mass or more. 10 parts by mass or less. A cured product, which is a cured product of the curable composition according to any one of claims 1 to 10.